CN114308049A - Growth catalyst for preparing carbon nano tube with high specific surface area - Google Patents
Growth catalyst for preparing carbon nano tube with high specific surface area Download PDFInfo
- Publication number
- CN114308049A CN114308049A CN202111554506.3A CN202111554506A CN114308049A CN 114308049 A CN114308049 A CN 114308049A CN 202111554506 A CN202111554506 A CN 202111554506A CN 114308049 A CN114308049 A CN 114308049A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon nanotube
- carbon
- specific surface
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 105
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000002482 conductive additive Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- -1 ethylene, propylene, ethanol Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Abstract
The invention discloses a growth catalyst for preparing carbon nanotubes with high specific surface area. In a first aspect of the present application, there is provided a carbon nanotube growth catalyst, comprising FexCoyMozAl is 0.3-0.6, 5-20, and x-y. The carbon nanotube growth catalyst according to the embodiment of the application has at least the following beneficial effects: the Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst provided by the embodiment of the invention comprises multiple components of iron, cobalt, molybdenum and aluminum, the catalyst can be directly used without high-temperature pretreatment, and the catalyst can be used for producing the catalyst with the specific surface area of more than 350m at a high rate2The/g carbon nano tube has excellent catalytic growth effect and has larger application prospect in the preparation of the carbon nano tube.
Description
Technical Field
The application relates to the technical field of carbon nanotubes, in particular to a growth catalyst for preparing carbon nanotubes with high specific surface area.
Background
Carbon Nanotubes (CNTs) are one-dimensional nanocarbon materials with a hollow tubular structure, consisting of carbon atoms arranged in a hexagonal lattice, having a diameter of about 1 to 100nm and a high aspect ratio. Theoretically, carbon nanotubes have superior tensile strength, excellent thermal conductivity, excellent electrical conductivity, and chemical stability. Due to its excellent physical and chemical properties, CNTs exhibit potential applications in the fields of composite materials, new energy, aerospace, biotechnology, electronics, semiconductors, and the like, and have been widely and deeply studied. Over the years of development, CNTs have achieved commercial applications in conductive plastics and battery conductive additives.
The synthesis method of the CNT mainly includes an arc discharge method, a laser evaporation method, and a chemical vapor deposition method. Among them, the arc discharge method and the laser evaporation method are not suitable for mass production of CNTs due to cost and equipment limitations, and in contrast, the chemical vapor deposition method becomes a main process for producing large-tonnage carbon nanotubes, and the specific methods of the chemical vapor deposition method are as follows: organic small molecules (such as ethylene, propylene, ethanol and the like) are catalyzed by a transition metal catalyst under the high-temperature condition to crack and deposit solid carbon nanotubes, hydrogen and the like.
CNTs can be classified into three types according to the number of tube walls: single-walled CNTs having a diameter of about 1 nm; double-walled CNTs having a diameter of about 1.4-3 nm; and multi-walled CNTs having a diameter of about 5 to 100 nm. In the process of multi-walled CNT synthesis, the problem is that as the number of walls of the multi-walled carbon nanotubes increases, the proportion of disordered graphite also increases, resulting in a decrease in the quality of the multi-walled carbon nanotubes. For this reason, the industry has been striving to reduce the number of walls of multi-walled CNTs and increase their specific surface area. In view of the preparation process of chemical vapor deposition, the transition metal catalyst has an important effect on the growth and structural control of CNTs, and thus, it is necessary to provide a growth catalyst capable of increasing the specific surface area of carbon nanotubes.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. To this end, the present application proposes a growth catalyst capable of increasing the specific surface area of the carbon nanotube.
In a first aspect of the present application, there is provided a carbon nanotube growth catalyst, comprising FexCoyMozAl is 0.3-0.6, 5-20, and x-y.
The carbon nanotube growth catalyst according to the embodiment of the application has at least the following beneficial effects:
the Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst provided by the embodiment of the invention comprises multiple components of iron, cobalt, molybdenum and aluminum, the catalyst can be directly used without high-temperature pretreatment, and the catalyst can be used for producing a specific surface area larger than 350m at a high rate during chemical vapor deposition2The/g carbon nano tube has excellent catalytic growth effect and has larger application prospect in the preparation of the carbon nano tube.
In a second aspect of the present application, there is provided a method for preparing a carbon nanotube growth catalyst, the method comprising the steps of:
providing a metal precursor solution, wherein the metal precursor solution comprises an iron source, a cobalt source, a molybdenum source and an aluminum source according to the stoichiometric ratio, and the stoichiometric ratio is required as follows: based on the molar weight of aluminum as 1, the molar weight of iron is x, the molar weight of cobalt is y, the molar weight of molybdenum is z, 0.3 to (x + y) to 0.6, 5 to (x + y)/z is 20, and x is less than or equal to y;
and mixing the metal precursor solution with a precipitator for reaction, and collecting the precipitate to obtain the carbon nano tube growth catalyst.
Wherein the metal precursor solution is a raw material solution containing the metal elements required by the carbon nanotube growth catalyst, and comprises FexCoyMozX represented by Al: y: z: 1, mixing the precursor solution and a precipitator to perform coprecipitation reaction, wherein metal elements are hydrolyzed to form precipitates, thereby obtaining the carbon nano tube growth catalyst. The precipitant is optionally capable of performing a coprecipitation reaction with the metal precursor solution, and includes but is not limited to at least one of ammonia, ammonium carbonate, ammonium bicarbonate, urea, ammonium fluoride, and the like.
It can be seen that the preparation method of the carbon nanotube growth catalyst provided in the embodiment of the present application selects multiple components including iron, cobalt, molybdenum and aluminum as raw materials, can complete the preparation without adding complexing agent and surfactant, has a simpler process, is beneficial to large-scale production, and can realize high-yield production of carbon nanotubes with large specific surface area by using the prepared growth catalyst.
It can be understood that the metal source and the precipitant are subjected to precipitation reaction to directly form hydroxide, and considering the chemical vapor deposition process for preparing the carbon nanotube, the five-membered metal hydroxide can actually be calcined and reduced under the high-temperature condition of vapor deposition to form a mixture or alloy of elementary substances of the five-membered metal to participate in the catalytic reaction. Therefore, the step of calcination reduction may be omitted or retained during the preparation of the catalyst. If the step of roasting reduction needs to be reserved, roasting can be carried out at 400-800 ℃, and further roasting is carried out at 400-700 ℃, 500-700 ℃ and 600-700 ℃.
In some embodiments of the present application, 0.3 ≦ (x + y) 0.5, or 0.375 ≦ (x + y) 0.6, or 0.375 ≦ (x + y) 0.5.
In some embodiments of the present application, 5 ≦ (x + y)/z ≦ 15, or 8 ≦ (x + y)/z ≦ 12, or (x + y)/z is about 10.
It will be appreciated that the above requirements for the stoichiometric ratios of x and y, and for the stoichiometric ratios of x, y and z, may be combined arbitrarily therefrom.
In some embodiments of the present application, the iron source, the cobalt source, and the aluminum source are each independently selected from the group consisting of nitrate, sulfate, chloride, and acetate.
In some embodiments of the present application, the molybdenum source is a molybdate salt including, but not limited to, at least one of ammonium molybdate, ammonium heptamolybdate.
In some embodiments of the present application, the precipitating agent is selected from at least one of ammonium carbonate, ammonium bicarbonate, and aqueous ammonia.
In some embodiments of the present application, the precipitant has a concentration of 1 to 4 mol/Kg.
In some embodiments of the present disclosure, the reaction temperature after adding the precipitant is 20 to 100 ℃, preferably 20 to 80 ℃, and 30 to 60 ℃.
In some embodiments of the present application, the precipitate is collected by filtering the precipitate and drying the filtered precipitate at a temperature of 80 to 200 ℃.
In a third aspect of the present application, there is provided a method for preparing a carbon nanotube, the method comprising the steps of:
and under the protective atmosphere, carrying out chemical vapor deposition on a carbon source under the action of a metal catalyst to obtain the carbon nanotube, wherein the metal catalyst is the carbon nanotube growth catalyst or the carbon nanotube growth catalyst prepared by the preparation method.
In some embodiments of the present application, the carbon source is an optional carbon source material in the form of a reaction gas, including but not limited to hydrocarbons in a gas phase at normal temperature, such as at least one of methane, ethane, ethylene, propane, propylene, acetylene, and the like. In some preferred embodiments, the carbon source is ethylene or propylene. It is understood that other commonly used carbon sources such as ethanol, acetone, dimethyl ether, etc. may also be used as the carbon source required in the preparation process.
In some embodiments of the present application, the reaction temperature of the chemical vapor deposition is 600 to 700 ℃, and more preferably 630 to 650 ℃; the reaction time of the chemical vapor deposition is 10 to 30 minutes, and more preferably 15 to 20 minutes.
In some embodiments of the present application, the protective atmosphere refers to protection from air, oxygen, and the like by inert gas, nitrogen, and the like, so as to avoid affecting the growth of the carbon nanotubes.
In a fourth aspect of the present application, there is provided a carbon nanotube produced by the foregoing production method. The carbon nanotubes prepared by the method have a particle size of at least 350m2The BET specific surface area/g shows that the aggregation form of the carbon nanotube is a twisted form when observed under a mirror, and the carbon nanotube has excellent properties in various aspects based on its high specific surface area.
In a fifth aspect of the present application, there is provided a composition comprising the aforementioned carbon nanotubes. The composition is formed by using the carbon nano tube as a main raw material or an additive component, including but not limited to conductive paste, an additive, a lubricant and the like.
The application aims at a four-component carbon nanotube growth catalyst and a specific surface larger than 350m2A winding type carbon nanotube in terms of/g. By optimizing the proportion relation of the components of the Fe-Co-Mo-Al catalyst and the generation of the carbon nano tubeThe carbon nanotubes with large specific surface area can be prepared with high yield for a long time and at high temperature, and can be used as a polymer conductive additive and a lithium ion battery anode conductive agent.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
FIG. 1 is a scanning electron microscope image of carbon nanotubes grown at 620 ℃ for 10 minutes in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of carbon nanotubes grown at 640 ℃ for 10 minutes in example 2 of the present invention.
FIG. 3 is a transmission electron microscope image of carbon nanotubes grown at 640 ℃ for 10 minutes in example 2 of the present invention.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
The following detailed description of embodiments of the present application is provided for the purpose of illustration only and is not intended to be construed as a limitation of the application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present number, and the above, below, within, etc. are understood as including the present number. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated. About is understood to mean floating up and down within the range of + -20%, + -15%, + -10%, + -8%, + -5%, + -3%, + -2%, + -1%, + -0.5%, + -0.2%, + -0.1% of the point values.
In the description of the present application, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The embodiment provides a Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst, and the preparation method comprises the following steps:
(1) taking Fe (NO)3)3·9H2O、Co(NO3)2·6H2O and Al (NO)3)3·9H2O is respectively dissolved in deionized water to prepare 1mol/Kg solution for later use. To obtain (NH)4)6Mo7O24·4H2Dissolving O in deionized water to prepare 0.1mol/Kg solution for later use. To obtain (NH)4)2CO3Dissolving in deionized water to prepare 2mol/Kg solution for later use.
(2) According to the element mole ratio of Fe: co: mo: al ═ 0.25: 0.25: 0.05: and 1, respectively weighing 20g, 40g and 80g of Fe, Co, Mo and Al precursor solutions, and mixing to obtain the metal precursor solution.
(3) A2L three-necked flask was charged with 200mL of deionized water and 150g of the prepared (NH)4)2CO3Stirring the solution, heating to 45 ℃, and slowly dripping the metal precursor solution. After the end of the dropwise addition, stirring was continued for half an hour, and the final pH was measured to be 8-8.5 using pH paper. Filtering to obtain a precipitate, washing the precipitate without deionized water, drying the precipitate in a drying oven at 120 ℃ for 24 hours, and grinding the dried product into fine powder to obtain the Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst.
The embodiment also provides a carbon nanotube, and the preparation method of the carbon nanotube comprises the following steps:
carbon nanotube growth experiments were performed in a horizontal fixed bed quartz reactor. The carbon nanotube growth catalyst prepared in this example was uniformly placed in a quartz boat, and the quartz boat was then pushed into the constant temperature zone of the tube furnace. The temperature was raised to the reaction temperature under nitrogen atmosphere, and then ethylene was introduced as a carbon source. And stopping introducing ethylene after reacting for a period of time, taking out the carbon nano tube after the temperature is reduced to room temperature in the nitrogen atmosphere, weighing, calculating the multiplying power, and measuring the specific surface area by a BET method.
According to the above preparation method, with different reaction temperatures and reaction times, the detection results of the finally prepared carbon nanotubes are shown in table 1:
TABLE 1 production rate and specific surface area results of carbon nanotubes under different experimental conditions of example 1
| Experimental number | Reaction temperature/. degree.C | Reaction time/min | Production multiplying power | Specific surface area/(m)2/g) |
| 1 | 600 | 10 | 14 | 344 |
| 2 | 610 | 10 | 16 | 352 |
| 3 | 620 | 10 | 19 | 362 |
| 4 | 620 | 15 | 24 | 351 |
| 5 | 630 | 10 | 22 | 356 |
| 6 | 640 | 10 | 25 | 355 |
| 7 | 660 | 10 | 35 | 345 |
Wherein, the production rate ═ (total weight of CNTs after reaction-weight of pre-reaction catalyst)/weight of pre-reaction catalyst;
the specific surface area of the CNTs was measured by the BET method. A larger BET specific surface area indicates that the CNT has a smaller diameter. When used as a conductive additive, CNTs with large specific surface area are added in a smaller amount.
Referring to fig. 1, it is an electron microscope image of the carbon nanotubes grown at 620 ℃ for 10 minutes in the above table, and it can be seen from the electron microscope image that the carbon nanotubes prepared in the examples of the present application have a significant "winding type" secondary aggregation morphology.
Referring to the detection results in Table 1, the specific surface area of more than 350m can be obtained within the reaction temperature of 610-640 DEG C2(ii) CNT in g. On the other hand, comparing the growth rates, it was found that the growth rate of CNTs gradually increased with increasing temperature; meanwhile, the growth rate of the carbon nano tube can reach 25 after 10 minutes of reaction time.
The specific surface area of the CNT and the number of the tube walls thereof have a direct relationship with the tube diameter, and the smaller the tube walls, the larger the specific surface area. The number of walls and the diameter of the tube are related to the particle size of the active component particles of the catalyst, and the smaller the particle size, the smaller the number of the walls of the obtained CNT, the smaller the tube diameter and the larger the specific surface area. The initial particle size of the catalyst active component particles is determined by a catalyst preparation method, but in the process of preparing the CNT by chemical vapor deposition, the particle size of the catalyst active component particles can grow gradually along with the reaction at a higher reaction temperature, so that the number of the CNT walls is increased, and the tube diameter is enlarged until the catalyst is deactivated; lowering the reaction temperature can slow down the growth of catalyst particles, but the contradiction is that the reduction of the reaction temperature leads to a slow growth rate of CNTs and a reduction in production efficiency. The catalyst prepared by the embodiment can reach the growth rate of about 25 at lower temperature in a shorter time, and simultaneously maintains the high specific surface area of the CNT.
Example 2
The embodiment provides a Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst, the preparation method of the catalyst is the same as that of embodiment 1, the molar ratio of elements is Fe: co: mo: al 0.125: 0.25: 0.0375: 1.
the experimental results of the carbon nanotubes prepared by the preparation method of example 1 using the above carbon nanotube growth catalyst at different reaction temperatures and reaction times are shown in table 2:
TABLE 2 production rate and specific surface area results of carbon nanotubes under different experimental conditions of example 2
| Experimental number | Reaction temperature/. degree.C | Reaction time/min | Production multiplying power | Specific surface area/(m)2/g) |
| 1 | 620 | 10 | 8.5 | 368 |
| 2 | 630 | 10 | 11 | 368 |
| 3 | 640 | 10 | 12 | 374 |
| 4 | 650 | 10 | 13 | 374 |
| 5 | 660 | 10 | 17 | 369 |
| 6 | 700 | 10 | 23 | 347 |
Referring to fig. 2 and 3, which are scanning electron microscope and transmission electron microscope images of carbon nanotubes grown at 640 ℃ for 10 minutes, it can be seen from fig. 2 that the carbon nanotubes prepared in this example are also "winding type". Referring to fig. 3, the diameter of the carbon nanotube prepared in example 2 of the present application is 10 to 20nm, wherein it can be clearly seen that the multi-layer structure is a typical multi-wall carbon nanotube, and the number of walls is approximately 8 or more.
Combining the results of Table 2 and Table 1, the production rate decreased with increasing the Co element ratio, but the specific surface area of the obtained CNT reached 370m, as compared with example 12And about/g.
Comparative example 1
The comparative example provides a quaternary carbon nanotube growth catalyst of Fe-Co-Mo-Al, which is different from that of example 1 in that the element molar ratio is Fe: co: mo: al ═ 0.25: 0.125: 0.0375: 1.
the experimental results of the carbon nanotubes prepared by the preparation method of example 1 using the above carbon nanotube growth catalyst at different reaction temperatures and reaction times are shown in table 3:
TABLE 3 production rate and specific surface area results of carbon nanotubes in different experimental conditions of comparative example 1
Compared with the embodiment 2, the comparative example 1 has the advantages that the molar ratio of Fe to Co is changed, so that the proportion of Fe is larger than that of Co, the specific surface area of the finally prepared CNT is lower, and is reduced by 50-70 m2/g。
Comparative example 2
The comparative example provides a Fe-Co-Mn-Mo-Al five-membered carbon nanotube growth catalyst, which is different from the catalyst in example 1 in that the element molar ratio is Fe: co: mn: mo: al ═ 0.3: 0.3: 0.09: 0.06: 1.
the experimental results of the carbon nanotubes prepared by the preparation method of example 1 using the above carbon nanotube growth catalyst at different reaction temperatures and reaction times are shown in table 4:
TABLE 4 production rate and specific surface area results of carbon nanotubes in different experimental conditions of comparative example 2
| Experimental number | Reaction temperature/. degree.C | Reaction time/min | Production multiplying power | Specific surface area/(m)2/g) |
| 1 | 620 | 10 | 13 | 303 |
| 2 | 640 | 10 | 20 | 300 |
| 3 | 660 | 10 | 17 | 279 |
Comparative example 2 compared with example 1, additional Mn element was added, but the specific surface area of the carbon nanotube prepared under the same conditions with the catalyst was still only 300m2The/g is even insufficient, and the reduction is obvious.
Comparative example 3
The comparative example provides a quaternary carbon nanotube growth catalyst of Fe-Co-Mo-Al, which is different from that of example 1 in that the element molar ratio is Fe: co: mo: al 0.125: 0.125: 0.025: 1.
the experimental results of the carbon nanotubes prepared by the preparation method of example 1 using the above carbon nanotube growth catalyst at different reaction temperatures and reaction times are shown in table 5:
TABLE 5 production rate and specific surface area results of carbon nanotubes in comparative example 3 under different experimental conditions
| Experimental number | Reaction temperature/. degree.C | Reaction time/min | Production multiplying power | Specific surface area/(m)2/g) |
| 1 | 620 | 10 | 3.2 | 300 |
| 2 | 640 | 10 | 4 | 318 |
| 3 | 660 | 10 | 5.4 | 316 |
| 4 | 680 | 10 | 4.9 | 290 |
The contents of Fe and Co in the catalyst of this comparative example were greatly reduced as compared with example 1, and the final catalyst was obtainedThe obtained CNT, like the other comparative examples, was still only 300m2About/g, the quality requirement of the high-quality multi-wall carbon nano-tube cannot be met.
It can be seen from the combination of the above test results of the examples and the comparative examples that the carbon nanotube growth catalyst disclosed in the examples of the present application is made of FexCoyMozAl, four elements. The catalyst can be prepared by coprecipitation reaction of a metal precursor solution and an alkali solution. When the proportion of each element satisfies the conditions of 0.3-0.6, 5-20, x-20, the specific surface area of the carbon nano tube obtained by the catalyst prepared by the catalyst preparation method participating in the chemical vapor deposition can reach 350m2More than g, the carbon nano tube belongs to winding type carbon nano tube. The carbon nano tube with high specific surface area can be used as a polymer conductive additive and a lithium ion battery positive electrode conductive agent, so that the battery performance is improved.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
Claims (10)
1. A carbon nanotube growth catalyst characterized by FexCoyMozAl is 0.3-0.6, 5-20, and x-y.
2. The preparation method of the carbon nano tube growth catalyst is characterized by comprising the following steps:
providing a metal precursor solution, wherein the metal precursor solution comprises an iron source, a cobalt source, a molybdenum source and an aluminum source according to a stoichiometric ratio, and the stoichiometric ratio is required as follows: based on the molar weight of aluminum as 1, the molar weight of iron is x, the molar weight of cobalt is y, the molar weight of molybdenum is z, 0.3 to (x + y) to 0.6, 5 to (x + y)/z is 20, and x is less than or equal to y;
and mixing the metal precursor solution with a precipitator for reaction, and collecting the precipitate to obtain the carbon nano tube growth catalyst.
3. The method according to claim 2, wherein the precipitant is at least one selected from the group consisting of ammonium carbonate, ammonium bicarbonate, and ammonia water.
4. The method of claim 2, wherein the iron, cobalt and aluminum sources are each independently selected from the group consisting of nitrate, sulfate, chloride and acetate.
5. The method of claim 2, wherein the molybdenum source is a molybdate.
6. The preparation method according to claim 2, wherein the reaction temperature after the precipitant is added is 20 to 100 ℃.
7. The method according to claim 2, wherein the precipitate is collected by filtering the precipitate and drying the filtered precipitate at a temperature of 80 to 200 ℃.
8. The preparation method of the carbon nano tube is characterized by comprising the following steps:
performing chemical vapor deposition on a carbon source under the action of a metal catalyst under a protective atmosphere to obtain the carbon nanotube, wherein the metal catalyst is the carbon nanotube growth catalyst in claim 1 or the carbon nanotube growth catalyst prepared by the preparation method in any one of claims 2 to 7.
9. A carbon nanotube produced by the production method according to claim 8.
10. A composition comprising the carbon nanotubes of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111554506.3A CN114308049A (en) | 2021-12-17 | 2021-12-17 | Growth catalyst for preparing carbon nano tube with high specific surface area |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111554506.3A CN114308049A (en) | 2021-12-17 | 2021-12-17 | Growth catalyst for preparing carbon nano tube with high specific surface area |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114308049A true CN114308049A (en) | 2022-04-12 |
Family
ID=81051876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111554506.3A Pending CN114308049A (en) | 2021-12-17 | 2021-12-17 | Growth catalyst for preparing carbon nano tube with high specific surface area |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114308049A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536007A (en) * | 2022-10-31 | 2022-12-30 | 山东大展纳米材料有限公司 | Few-wall array carbon nanotube and growth catalyst precursor and preparation method thereof |
| CN115608372A (en) * | 2022-09-15 | 2023-01-17 | 河南国碳纳米科技有限公司 | Iron-cobalt-based catalyst, carbon nano tube and preparation process thereof |
| CN115650211A (en) * | 2022-09-15 | 2023-01-31 | 河南国碳纳米科技有限公司 | Carbon nano tube and two-section type preparation process thereof |
| CN115672327A (en) * | 2022-11-10 | 2023-02-03 | 无锡碳谷科技有限公司 | High specific surface area superfine nano catalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827027A (en) * | 2012-01-11 | 2014-05-28 | Lg化学株式会社 | Carbon nanotubes and method for manufacturing same |
-
2021
- 2021-12-17 CN CN202111554506.3A patent/CN114308049A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827027A (en) * | 2012-01-11 | 2014-05-28 | Lg化学株式会社 | Carbon nanotubes and method for manufacturing same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115608372A (en) * | 2022-09-15 | 2023-01-17 | 河南国碳纳米科技有限公司 | Iron-cobalt-based catalyst, carbon nano tube and preparation process thereof |
| CN115650211A (en) * | 2022-09-15 | 2023-01-31 | 河南国碳纳米科技有限公司 | Carbon nano tube and two-section type preparation process thereof |
| CN115608372B (en) * | 2022-09-15 | 2024-03-26 | 河南国碳纳米科技有限公司 | Iron-cobalt-based catalyst, carbon nanotube and preparation process thereof |
| CN115536007A (en) * | 2022-10-31 | 2022-12-30 | 山东大展纳米材料有限公司 | Few-wall array carbon nanotube and growth catalyst precursor and preparation method thereof |
| CN115536007B (en) * | 2022-10-31 | 2024-02-20 | 山东大展纳米材料有限公司 | Few-wall array carbon nano tube, growth catalyst precursor thereof and preparation method |
| CN115672327A (en) * | 2022-11-10 | 2023-02-03 | 无锡碳谷科技有限公司 | High specific surface area superfine nano catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114308049A (en) | Growth catalyst for preparing carbon nano tube with high specific surface area | |
| CN110801843B (en) | Two-stage method for preparing high-magnification carbon nano tube with superfine tube diameter, catalyst and preparation method thereof | |
| US7470418B2 (en) | Ultra-fine fibrous carbon and preparation method thereof | |
| WO2019113993A1 (en) | Carbon nanotube and method for fabrication thereof | |
| CN114570380A (en) | Catalyst for growing ultrahigh specific surface area and few-wall carbon nano-tube and application thereof | |
| CN111495381A (en) | Preparation method of flaky catalyst, flaky catalyst and application of flaky catalyst in preparation of superfine carbon nano tube | |
| CN113058605B (en) | Catalyst for carbon nanotube and preparation method and application thereof | |
| JP2015529558A (en) | Supported catalyst, method for producing the same, and secondary structure of carbon nanostructure produced using the catalyst | |
| CN111495380B (en) | Preparation method of carbon nanotube catalyst and carbon nanotube | |
| CN109665512A (en) | A kind of preparation method of multi-walled carbon nanotube | |
| Zhao et al. | Catalytic anisotropy induced by multi-particles for growth of carbon nanocoils | |
| CN1326613C (en) | Compound metal oxide catalyst for preparing carbon nanometer tube with high production rate and its preparing process | |
| JP2022530905A (en) | Carbon-Carbon Nanotube Hybrid Material and Its Manufacturing Method | |
| CN111943722A (en) | Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof | |
| KR101679693B1 (en) | Method for preparing carbon nanotube and hybrid carbon nanotube composite | |
| CN110252304B (en) | Iron-based catalyst, preparation method and application thereof, carbon nano tube and preparation method thereof | |
| CN1236849C (en) | Aluminium oxide carrier metal oxide catalyst used for preparing carbon nanometer pipe and its preparation method | |
| CN112371131A (en) | Carbon nano tube growth catalyst, preparation method thereof and preparation method of carbon nano tube | |
| JP2004324004A (en) | Carbon fiber and method for producing the same | |
| JP2017039099A (en) | Catalyst for carbon nanotube synthesis | |
| KR20130049737A (en) | Double wall carbon nanotue and method for preparing same | |
| KR101180435B1 (en) | Catalyst for Synthesizing multi-walled Carbon Nanotube having high conductivity and dispersibility and manufacturing method thereof | |
| CN113663690B (en) | Catalyst for preparing small-diameter single-wall carbon nano tube, preparation method and application | |
| CN113101981B (en) | Preparation method of catalyst for preparing carbon nanotube | |
| CN115805076B (en) | Catalyst and preparation method thereof, array carbon nanotube and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |